Unsymmetrical bis-(anthraquinoneazole)-azobiphenyl yellow vat dyes



United States Patent Ofiice 3367328 Patented F eb. 6, 1958 3,367,928 The primary object of the present invention is to UNSYMMETRICAL BIS (ANTHRAQUINONE provide new compounds of the bis(anthraquinone-azole)- AZOBIPHENYL YELLOW VAT azobiphenyl class which give strong yellow dyeings on vegetal fibers from the vat, having good. fastness propg f g pggf gl gg %'g; g z g gggg 5 erties (to light, to Washing and to bleaching treatments) of New York and which have excellent stability to high temperatures. N Drawing Filed 2 19 s 422907 Another object of the present invention is to provide 8 Claims. (Cl. 260157) new bis-(anthraquinone-azole)-azobiphenyl compounds which possess relatively good stability in the alkaline hy- 10 drosulfite vat.

ABSTRACT OF THE DISCLOSURE A further object of the present invention is to provide Unsymmetrical bis-(anthraquinone-azole)-azo biphenyl a Process for Preparing Such bis-(anthfaquillofle-alole)- compounds of the formula azobiphenyl compounds.

wherein X is O or S, R is H or lower alkyl, 12 is whole Other objects of the invention in part will be obvious number from 1 to 3 and the anthraquinone nuclei A and and in part will appear hereinafter.

B may each be further substituted by 1 to 3 chloro, bromo, According to the present invention the above objects loweralkyl, lower alkoxy, perchloro, or perbromo, lower are accomplished by the provision of compounds of the alkyl, lower alkylol amino aryl and aroylamino of no above class which are unsymmetrical bis-(anthraquinonemore than 6 ring carbon atoms substituents which give azole)-azobiphenyl compounds in which (1) a 6,11-distrong yellow dyeings on vegetal fibers from the vat and oXo-1H-anthra[l,2-d]imidazo1yl radical is linked through which dyeings have good fastness properties to light, to the 2-carbon atom of the imidazolyl radical to one of washing and to bleaching treatments and have excellent 5 the biphenyl radicals of an azobiphenyl nucleus and (2) stability to high temperatures. a 5,l0-dioxo-anthra[2,3-d1oxazolyl or thiazolyl radical (that is, a radical in which the heterocyclic nucleus contains an element in addition to nitrogen which is one of This invention relates to vat dyestuffs of the anthrathe first two members of Group VI of the Periodic Table) quinone series which dye vegetal fibers yellow shades. It is linked through the 2-carbon atom to the other biphenyl relates more particularly to novel vat dyestuffs of that radical of the azobiphenyl nucleus. class of bis-(anthraquinone-azole)-azobiphenyl com- Preferred compounds of the present invention are pounds in which two anthraquinone-azole radicals are the unsymmetrical bis-(anthraquinone-azole)-azobiphenyl linked, respectively, through the carbon atoms of the compounds of said type in which the antraquinone-azole azole radicals to carbon atoms of an azobiphenyl nucleus. radicals are respectively linked through their Z-carbon Anthraquinone-azole compounds of said class are disatoms to the 4- and 4'-positions of the respective biphenyl closed in US. Patent 2,175,803. They are usually preradicals of the azobiphenyl nucleus, and especially those pared by condensing azobiphenyl-dicarbonyl chloride with in which oxygen forms a part of the second azole radical. an aminoanthraquinone having, adjacent to the amino 1 have discovered that the unsymmetrical bis-(anthragroup, a halogen atom or a hydroxyl, mercapto or amino 5() quinone-azole)-azobiphenyl compounds of the present ingroup; and subjecting the resulting intermediate product vention, and especially those of the latter type, are vat to ring-closure and conversion to the corresponding symdyestuffs which dye vegetal fibers yellow colorations (i.e., metrical bis-(anthraquinone-imidazole, -oxazole or 'thiayellow to reddish-yellow or orange) which have high zole)-azobiphenyl compound. The known imidazole comtinctorial strength, which are fast to light, to washing pounds of said class, and especially those which produce and to bleaching treatments, and which in the reduced yellow shades on vegetal fibers, are subject to one or state have excellent stability to high temperatures. more deficiencies, however, which have limited their use- This result is surprising because the symmetrical bisfulness as vat dyes; for example, poor tinctorial strength, (anthra-imidazolyl)-azobiphenyls suffer from inadequate and poor fastness properties (to light or to washing or to tinctorial strength and fastness properties and instability bleaching treatments). Moreover, certain of them are at high temperatures. deficient in application properties; they are unstable when The unsymmetrical bis-(anthraquinone-azole)-azo-bidyed at high temperatures being of relatively poor staphenyl compounds of the present invention are represented bility in the alkaline hydrosulfite vat. by the following Formula I:

ll 0 N=N C=N- II Koo Km B X) R. R. t. i. \of Y o wherein X is selected from the group consisting of O and S,

R is selected from the group consisting of hydrogen, halogen and lower alkyl and lower alkoxy radicals, and

n is a whole number from 1 to 3, and the anthraquinone nuclei A and B may each be further substituted by 1 to 3 substituents selected from the group consisting of halogen and lower alkyl, perhalo lower alkyl, lower alkoxy, alkylolamine, aryl and aroylamino radicals.

The term lower, as employed herein (including the claims) in connection with alkyl and related radicals, denotes radicals having 1 to 6 carbon atoms.

Preferred compounds of the present invention, in which the anthraquinone-azole radicals are linked respectively through their 2-carbon atoms to the terminal para-positions of the respective biphenyl radicals of the azobiphenyl nucleus (herein termed the 4,4'-positions of the azobiphenyl radical), are represented by the following Formulas II and III, wherein R and n have the above meaning and the anthraquinone nuclei A and B may each be further substituted as set out above:

(I) N H O N I] B A Rn Ra Ra Ru 0 0 The compounds of the present invention can be synthesized in several ways.

Thus, they can be obtained by condensing a (6,11-dioxo-lH-anthra[1,2-d]imidazol-2-yl)azobiphenyl carbonyl halide (preferably the chloride or bromide) with a betaaminoanthraquinone having a halogen, hydroxyl or mercapto substituent in the adjacent beta position; and simultaneously or subsequently converting the resulting N-2- anthraquinonyl-(6,1l-dioxo-1H-anthra[ l,2-d]imidazol 2- yl)azobiphenylcarboxamide to the oxazole or thiazole.

For example, a (6,ll-dioxo-lH-anthra[l,2d]imidazol- 2-yl)azobiphenyl-carbonyl chloride having the following Formula IV wherein R and n have the above meaning, and the anthraquinone nucleus A may be substituted as indicated above,

can be heated with a substantially equimolecular proportion of a 2-arninoanthraquinone having the following Formula V Y 0 Y V wherein D represents a member selected from the group consisting of chlorine, bromine, hydroxy and thiol,

Q represents a member selected from the group con- 0 N H N III and the resulting N-2-anthraquinonyl-(6,1l dioxo 1H- anthra[l,2-d]imidazol 2 yl)azobiphenylcarboxamide is converted to the oxazole or thiazole; for example, by

phenyl-carbonyl halide can itself be obtained by condensing an azobiphenyl-dicarbonyl halide with a 1,2-diamino-anthraquinone, and simultaneously or subsequently ring closing the resulting N-(amino-anthraquinonyl)carbamoyl-azobiphenyl-carbonyl halide, obtained as condensation product, to the imidazole.

Ring-closure of. the latter condensation product to the imidazole can be carried out prior to the condensation of the resulting intermediate imidazolyl azobiphenyl-carbonyl chloride with the 2-aminoanthraquinone represented by Formula V; or it can be carried out in conjunction with formation of said imidazolyl azobiphenyl compound. Similarly, the condensation product resulting from the reaction of imidazolyl azobiphenyl-carbonyl chloride with the 2-amino-anthraquinone having a halogen, hydroxyl or mercapto (thiol) substituent in the 3-position can be converted to the oxazole or thiazole by ring-closure during the latter condensation, or subsequently thereto, or simultaneously With the ring-closure reaction forming the imidazole.

Accordingly, in carrying out the preparation of the unsymmetrical bis-(anthraquinone-azole)-azobiphenyl compounds of the present invention in accordance with the preferred procedure, an azobiphenyl-dicarbonyl chloride, represented by the following Formula VI:

wherein R and n have the above meaning,

CIOC C001 is condensed, first with a substantially equimolecular quantity of a 1,2-diaminoanthraquinone having the following Formula VII:

VII

wherein Q and Y have the above meaning,

followed by condensing the resulting aminoanthraquinonylamino-azobiphenyl-carbonyl chloride with a substantially equimolecular proportion of a 2-aminoanthraquinone having the above Formula V, and forming the respective imidazole and oxazole or thiazole rings simultaneously or step-wise.

In general the condensation is carried out by heating the above reactants in an inert organic medium which is liquid at the reaction temperature, such as, nitrobenzenes, nitrotoluenes, mono-, -di and -tri chlorobenzenes, and preferably with the aid of an organic acid binding agent; for example, an organic base such as pyridine, quinoline, collidine, dimethylaniline, and the like, or a salt such as sodium and potassium carbonates, sodium and potassium acetates, and the like.

The condensation reaction(s) can be carried out over a broad range of temperatures. Thus temperatures between 100 and 200 C. can be used although it is preferred to use a temperature within the range of about 120 to about 150 C. for this reaction. Temperatures above 200 C. are not advisable since they lead to increased amounts of by-products; while at temperatures below 100 C., the rate of reaction becomes inordinately slow.

Ring closure of the amines is etfected by heating the condensation product(s) at a more elevated temperature (i.e., above 150 C., preferably between 160 and 220 C.), and preferably in the presence of catalysts (such as, copper salts) and acid binding agents (such as, sodium carbonate or potassium acetate).

The ring closures forming the respective heterocyclic nuclei can be carried out separately or at the same time; and, if desired, the condensation and ring closure reactions can both be effected :by heating the reactants at a temperature within the range from about 160 C. to about 225 C.

The following compounds are representative of dyestuffs of the invention:

4 (6,11 dioxo-lH-ant-hraPLZ-d]imidazol-2-yl)4-(5,

l0-dioxo-anthr-a [2, 3d] thiazol-Z-yl) azobiphenyl 4 (8 chloro-6,11-dioxo-lH-'anthra[1,2 d]imidazol-2- yl) 4'(5,10-dioxo-anthra[2,3-d]-oxazol-2-yl)azobiphenyl 4 (6,1 1 dioxo 1H-anthra[l,-2-d]imidazol-2-yl)-4- (6 butoxy 5,10 dioxo-anthra[2,3-d]oxazol-Z-yl) azobiphenyl 4 (6,11 dioxo-lH-anthra[l,2d]imidazoi-2-yl)-4'- 5,10 dioxo ant-hra[2,3 d]thiazol 2 yl)3,3'-'dimethyl-azobiphenyl The following amino-anthraquinones exemplify the broad classes of 1, 2-diarnino-anthraquinones, represented by above Formula V II, and 2-amino-3-substitute-d-anthraquinones represented by above Formula V, which are suitable for producing the compounds of the present invention by the processes of this invention:

1,Z-diaminoanthraquinone 1,2-diamino-3 br-omoanthraquinone 1,2-diamino-'4-oh1oroanthraquinone 1,2-diamino-5bromoanthr-aquinone 1,2adiamino-6-chloroanthraquinone 1,Z-diamin'o-S,8-dichloroanthraquinone 1,Z-diam-ino-S-methylanthraquinone 1,Z-diamino-8-ethoxyanthraquinone l,Z-diamino-5-benzamidoanthraquinone -2-a-mino-3-chloroanthr-aquinone 2-amino-3-chlor0-1-methylanthraquinone 2-amino3-mercaptoanthraquinone 2-amino-3-mercapto-8ethoxyanthraquinbne 2-amino-3-bromo-5-ethy1anthraquinone 2-amino-3 -bromo-4-methoxyanthraqumone =2-amino3-mercapto-1 benzamidoanthraquinon-e The products obtained by the above processes of the invention can be conditioned .for use in dyeing or printing in the known manner, for example, by acid pasting, salt grinding, sand grinding and the like. 'If desired, the crude products also may be subjected to oxidation and other purification treatments; for example, with sodium dichromatc, aqueous alkali metal hydrochlorite, and the like, as is customary in the manufacture of vat dyestuifs.

The following examples describe specific embodiments of the invention and illustrate the best method contemplated for carrying it out; but they are not to be interpreted as limiting the invention to all details thereof, since changes can be made without departing from the scope of the invention. The temperatures are in degrees centigrade and the parts and percentages are by weight, unless designated as parts by volume. Where parts are by volume, the amount signifies the volume occupied by the same number of parts by weight of Water at 4 C.

EXAM PLE 1 Part 1.--A mixture of 11.5 parts of azobiphenyl-4,4'- 'dicarbonyl chloride, 6.0 parts of 1,2-diaminoanthraqu-inone, 0.2 part of pyridine and about 420 parts of dry nitrobenzene is agitated and heated to and held for about 3 hours at 135 to Then 7.0 parts of-Z-amino- 3-chloro-anthraquin'one are added, and the mixture is heated to and maintained at 135 to 140 for about 18 hours to complete formation of the intermediate unsymmetrical bis (aminoant hr-aqu inonyl carbramoyD-azobiphenyl compound. Then, to convert it to the corresponding unsymmetrical product without isolation from the reaction mass, '12 parts of anhydrous potassium acetate, 12 parts of sodium carbonate, 0.2 part of oupric acetate and 0.2 part of cuprous chloride are added to the mass, which then is heated to boiling and refluxed (205 to 210) for about 1-2 hours. The resultant mixture is cooled to about '7 8 80, the slurry of product is filtered, and the filter cake excellent fastness to light and to washing. The vat is is washed with nitrobenzene and then with alcohol. The stable to heating at high temperatures. The resulting prodwashed cake is dried. uct corresponds to the formula it 11 N N C C N% H 0 IX Part 2.For purposes of conditioning and purifying EXAMPLE 2 The Tesulting Crude [L l 20 The process of Example 1 is repeated using 6.9 parts 2 Y l -y of 1,Z-diamino-6-chloroanthraquinone in place of the 1,2- phenyl, 1 part thereof is dissolved in about 13 parts of diaminoanthraquinone. The resulting dy-estufl correspond-s 98% sulfuric acid with agitation at 15 to for 2 to to the formula N ll 3 hours; the resultant solution is drowned in about 130 40 Its dyeings on cotton are slightly greener than those o-bparts of cold Water; 1 part of sodium bichromate tained with the dyestulf of Example 1. The fastness char- (Na Cr C J2xH 0) is added; and the slurry is heated to acteristics are equal to those obtained with said dyestuff. 95 to 100, held at said temperature for about 16 hours,

cooled to be low 80, and filtered. The filter cake is washed EXAMPLE 3 acid-(free with water; the washed cake is reslurried in Repetition of the procedure of Example 1 but using about 130 parts of Water containing 1 part of sodium 7.0 parts of 2-amino-3-mercaptoanthraquinone instead of carbonate and, after heating to 75 to 80, about 2 parts the 2-amino-3-chloroanthraquinone, gives the correspondof aqueous sodium hypochlorite (containing about 10% ing unsymmetrical product corresponding to the formula active chlorine) are added and the mixture is agitated Its dyeings on cotton have comparable fastness qualiat 75 to 80 for about 6 hours. The excess hypochlorite ties but are distinctly redder in shade than the dyeings is destroyed by the addition of sodium bisulfite, the slurry obtained with the dyestutl of Example 1.

is filtered, and the filter cake is Washed alkali-free with It will be realized by those skilled in the art that the water. invention is not limited to the details of the foregoing Part 3 .The washed filter cake obtained in accordance description and that changes can be made without departwith Part 2 of this example is converted to a dyestuif ing from the scope of the invention. paste by stirring it with 1% of a sulfionated naphthalene- Thus instead of the amino-anthraquinones and azobiformaldehyde condensation product (Tamol N). When phenyl-dicarbonyl chloride employed in the above specotton is dyed with the resulting dyestufi paste in analkacific examples, nrolecula-rly equivalent amounts of others line hydrosulfite vat in the usual manner, bright yellow of the specific anthraquinones and azobiphenyl-dicarbonyl dyeings are obtained having high tinctorial strength and halides disclosed above may be substituted in practicing the processes of the above specific examples. Further, the specific proportions, temperatures and reagents employed in the specific examples can be varied, as indicated in the above disclosure.

I claim:

1. Unsymmetrical bis anthraquinone azole)-azobiphenyl compounds represented by the formula:

wherein X is selected from the group consisting of O and S,

R is selected from the group consisting of hydrogen and lower alkyl radicals,

n is a whole number from 1 to 3, and the anthraqu-inone nuclei A and B each may be further substituted by 1 to 3 substituents selected from the group consisting of chlorine, bromine, lower alkyl, perchloro and perbromo lower alkyl, lower alkoxy, lower alkyloamino, aryl and aroylamino of no more than 6 ring carbon atoms.

2. A11 unsymmetrical his (anthraquin'one-azole)-azobiphenyl compound as defined in claim 1 wherein X is oxygen, R is hydrogen, and the vanthraquinone nuclei A and B may be further substituted by one to three substituents selected from the group consisting of chlorine, bromine, 'lowver alltyl, and lower alkoxy.

3. An unsymmetrical bis (anthraquinone-azo le)-azobiphenyl compound as defined in claim 1 wherein X is sulfur, R is hydrogen, and the anthraquinone nuclei A and B may be further substituted by one to three substituents selected from the group consisting of chlorine, bromine, lower alkyl and lower alkoxy.

4. The compound 4 (6,11 dioxodH-anthraE-LZ-d] imidazol 2-yl)-4'-(5,10-dioxoanthra[2,3-d]oxazol-Z-yl) azobiphenyl.

5. The compound 4 (6,1-1 dioxo-lH-anthra[l,2-d] imidazol 2-yl)-4'-(5,l0' dioxoanthra[2,3-d]thiazol-Z-yl) azobiphenyl.

6. The compound 4 (8 chl oro-6,lil-dioxo-lfl-anthra [1,2-d1imidazol 2 yl) 4'-(5,1G-dioxo-anth-ra[2,3-d] oxaz-ol-Z-yl) azobiphenyl.

7. The compound 4 (6,1:1 diox0-1H-:anthra[1,2-d] imidazol 2 yl)-4-( 6-butoxy-5,10-dioxo-anthra[2,3-d] oxazol-Z-y-l)azo biphenyl.

8. The compound 4 (6,11 diox-o-lH-anthra[1,2-d] imidazol 2 yl)-4-(5,10-dioxoanthra[3,3-d]thiazol-Z- yl) -3,3 '-dimethyl-azob=iphenyl.

References Cited UNITED STATES PATENTS 2,559,673 7/1951 Schroeder et a1. 260-157 2,601,100 6/4952 Deinet 26%157 2,719,840 10/1955 Deinet 260-157 FLOYD D. H-IGEL, Primary Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3 ,367 ,928 February 6 1968 Walter R. Demler It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, line 44, for "antraquinone" read'" anthraquinone T columns 3 and 4 the left-hand portion of the formula III should appear as shown below instead of as in the patent:

column 4, lines 5 to 10, the formula should appear as shown below instead of as in the patent:

column 6 line 14 for '5 ,l0" read (5 ,10- columns 7 and 8 the left -hand portion of formula X,"should appear as shown below instead of as in the patent:

columns 9 and 10 claim 1 the formula should appear as shown below instead of as in the patent N=N N o m H R O 1L1 n n n Rn 0 oh f O Signed and sealed this 22nd day of July 1969.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, Q Attesting Officer Commissioner of Patent 

